AU637852B2 - Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices - Google Patents
Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices Download PDFInfo
- Publication number
- AU637852B2 AU637852B2 AU67671/90A AU6767190A AU637852B2 AU 637852 B2 AU637852 B2 AU 637852B2 AU 67671/90 A AU67671/90 A AU 67671/90A AU 6767190 A AU6767190 A AU 6767190A AU 637852 B2 AU637852 B2 AU 637852B2
- Authority
- AU
- Australia
- Prior art keywords
- deposition
- amorphous silicon
- hydrogenated amorphous
- group
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 230000008021 deposition Effects 0.000 title claims abstract description 166
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 121
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 92
- 239000000956 alloy Substances 0.000 title claims abstract description 92
- 239000002019 doping agent Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000004065 semiconductor Substances 0.000 title claims description 26
- 239000000463 material Substances 0.000 title abstract description 70
- 239000000203 mixture Chemical group 0.000 claims abstract description 82
- 125000004429 atom Chemical group 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 34
- 150000002367 halogens Chemical group 0.000 claims abstract description 32
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims description 174
- 239000007789 gas Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 33
- 150000002431 hydrogen Chemical group 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011737 fluorine Chemical group 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 34
- 229910052732 germanium Inorganic materials 0.000 description 33
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 32
- VJFOQKOUHKDIGD-UHFFFAOYSA-N [GeH3][SiH3] Chemical compound [GeH3][SiH3] VJFOQKOUHKDIGD-UHFFFAOYSA-N 0.000 description 31
- 229910000077 silane Inorganic materials 0.000 description 29
- 239000010408 film Substances 0.000 description 25
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 22
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- HVXTXDKAKJVHLF-UHFFFAOYSA-N silylmethylsilane Chemical compound [SiH3]C[SiH3] HVXTXDKAKJVHLF-UHFFFAOYSA-N 0.000 description 19
- 229910000078 germane Inorganic materials 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 229910052796 boron Inorganic materials 0.000 description 14
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 13
- 229910000927 Ge alloy Inorganic materials 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000004678 hydrides Chemical class 0.000 description 10
- 238000010348 incorporation Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 229910052753 mercury Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 229910015900 BF3 Inorganic materials 0.000 description 7
- -1 Silicon-Germanium Hydrides Chemical class 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910000878 H alloy Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 6
- 238000005695 dehalogenation reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910001339 C alloy Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- ISYBXVAUXYUVPO-UHFFFAOYSA-N trisilylarsane Chemical compound [SiH3][As]([SiH3])[SiH3] ISYBXVAUXYUVPO-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- VXGHASBVNMHGDI-UHFFFAOYSA-N digermane Chemical compound [Ge][Ge] VXGHASBVNMHGDI-UHFFFAOYSA-N 0.000 description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 3
- 239000011491 glass wool Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- BHMLFPOTZYRDKA-IRXDYDNUSA-N (2s)-2-[(s)-(2-iodophenoxy)-phenylmethyl]morpholine Chemical compound IC1=CC=CC=C1O[C@@H](C=1C=CC=CC=1)[C@H]1OCCNC1 BHMLFPOTZYRDKA-IRXDYDNUSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- CZIXLYVYYWZJEG-UHFFFAOYSA-N bromo(silylmethyl)silane Chemical compound [SiH3]C[SiH2]Br CZIXLYVYYWZJEG-UHFFFAOYSA-N 0.000 description 2
- VQPFDLRNOCQMSN-UHFFFAOYSA-N bromosilane Chemical compound Br[SiH3] VQPFDLRNOCQMSN-UHFFFAOYSA-N 0.000 description 2
- FTYZKCCJUXJFLT-UHFFFAOYSA-N bromosilicon Chemical compound Br[Si] FTYZKCCJUXJFLT-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- LRZMJFRZMNWFKE-UHFFFAOYSA-N difluoroborane Chemical compound FBF LRZMJFRZMNWFKE-UHFFFAOYSA-N 0.000 description 2
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical compound F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 2
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 2
- 229910052986 germanium hydride Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- KSMLIIWEQBYUKA-UHFFFAOYSA-N 4-(methylamino)-3-nitrobenzoic acid Chemical compound CNC1=CC=C(C(O)=O)C=C1[N+]([O-])=O KSMLIIWEQBYUKA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YVYWIKPMOJRDEX-UHFFFAOYSA-N F[Si](F)(F)[Ge]([Si](F)(F)F)([Si](F)(F)F)[Si](F)(F)F Chemical compound F[Si](F)(F)[Ge]([Si](F)(F)F)([Si](F)(F)F)[Si](F)(F)F YVYWIKPMOJRDEX-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910000979 O alloy Inorganic materials 0.000 description 1
- 229910008310 Si—Ge Inorganic materials 0.000 description 1
- BMSYAGRCQOYYMZ-UHFFFAOYSA-N [As].[As] Chemical compound [As].[As] BMSYAGRCQOYYMZ-UHFFFAOYSA-N 0.000 description 1
- KPSZQYZCNSCYGG-UHFFFAOYSA-N [B].[B] Chemical compound [B].[B] KPSZQYZCNSCYGG-UHFFFAOYSA-N 0.000 description 1
- JIMODRYHNQDMSX-UHFFFAOYSA-N [GeH2].[Si] Chemical class [GeH2].[Si] JIMODRYHNQDMSX-UHFFFAOYSA-N 0.000 description 1
- ROZUYFMKAHJYEW-UHFFFAOYSA-N [Sn].[Ge].[Si].[C] Chemical compound [Sn].[Ge].[Si].[C] ROZUYFMKAHJYEW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000001590 germanediyl group Chemical group [H][Ge]([H])(*)* 0.000 description 1
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- PPMWWXLUCOODDK-UHFFFAOYSA-N tetrafluorogermane Chemical compound F[Ge](F)(F)F PPMWWXLUCOODDK-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- OJSIFXHCRMUSJO-UHFFFAOYSA-N trifluoro-[tris(trifluorosilyl)methyl]silane Chemical compound F[Si](F)(F)C([Si](F)(F)F)([Si](F)(F)F)[Si](F)(F)F OJSIFXHCRMUSJO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
- H01L31/204—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table including AIVBIV alloys, e.g. SiGe, SiC
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Silicon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Compounds having the formula (MX3)n M'X4-n wherein M and M' are different Group 4A atoms, at least one of M and M' is silicon, X is hydrogen, halogen or mixtures thereof, and n is an integer between 1 and 4, inclusive, are useful as deposition feedstock materials in the formation of hydrogenated amorphous silicon alloys useful in the fabrication of photovoltaic and other electronically active devices. Dopants having the formula (SiX3)m L X3-m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony and bismuth, X is hydrogen, halogen or mixtures thereof and m is an integer between 1 and 3, inclusive, are useful in the fabrication of negatively-doped hydrogenated amorphous silicon alloys useful in the fabrication of photovoltaic and other electronically active devices. Dopants having the formula YJX2 wherein Y is halogen or carbonyl, J is a Group 3A atom and X is hydrogen, halogen or mixtures thereof, are useful in the formation of postively-doped hydrogenated amorphous silicon alloys useful in the fabrication of photovoltaic and other electronically active devices.
Description
637852
AUSTRALIA
PATENTS ACT 1952 COMPLETE SPECIFICATION Form
(ORIGINAL)
FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: SOLAREX CORPORATION 1335 PICCARD DRIVE
ROCKVILLE
MARYLAND 20805
U.S.A.
Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.
*r Complete Specification for the invention entitled: DEPOSITION FEEDSTOCK AND DOPANT MATERIALS USEFUL IN THE FABRICATION OF HYDROGENATED AMORPHOUS SILICON ALLOYS FOR PHOTOVOLTAIC DEVICES AND OTHER SEMICONDUCTOR DEVICES The following statement is a full description of this invention including the best method of performing it known to me:- BACKGROUND OF THE INVENTION The present invention relates to hydrogenated amorphous silicon alloys useful in the fabrication of photovoltaic devices and other semiconductor devices.
It is desirable to include carbon or germanium atoms in hydrogenated amorphous silicon alloys in order to adjust their optical bandgap. For example, carbon has a larger bandgap than silicon and thus inclusion of carbon in a hydrogenated amorphous silicon alloy increases the alloy's bandgap. Conversely, germanium has a smaller bandgap than silicon and thus inclusion of germanium in a hydrogenated amorphous silicon alloy decreases the alloy's bandgap.
Similarly it is desirable to incorporate boron or phosphorous atoms in hydrogenated amorphous silicon alloys in order to adjust their conductive properties. Including boron in a hydrogenated amorphous silicon alloy creates a positively doped conductive region. Conversely, including phosphorous in a hydrogenated amorphous silicon alloy creates a negatively doped conductive region.
20 Hydrogenated amorphous silicon alloy films are prepared by deposition in a deposition chamber. Heretofore, in preparing hydrogenatei' amorphous silicon alloys by deposition in a deposition chamber, carbon, germanium, boron or phosphorous have been incorporated into the alloys by including in the deposition gas mixture carbon, germanium, boron or phosphorous' containing gases such as methane (CH 4 germane (GeH 4 germanium tetrafluoride (GeF 4 higher order germanes such as digermane (Ge 2
H
6 diborane (B 2
H
6 or phosphine (PH 3 See for example, U.S. Patent Nos, 4,491,626, 4,142,195, 4,363,828, 4,504,518, 4,344,984, 4,435,445, and 4,394,400. A drawback of this practice, however, is that the way in which the carbon, germanium, boron or phosphorous atoms are incorporated into the hydrogenated amorphous silicon alloy is not controlled. That is, these elements are incorporated into the resulting alloy in a highly random manner thereby increasing the likelihood of undesirable chemical bonds.
SI
Summary of the Invention According to the present invention, there is provided a process for preparing a negatively-doped hydrogenated amorphous silicon alloy by deposition of a negatively-doped hydrogenated amorphous silicon alloy film onto a substrate in a deposition chamber comprising the step of introducing into the deposition chamber during deposition a deposition gas mixture which includes one or more dopants having the formula: (SiX L X 3m 3-m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
Preferably in said process, L is phosphorous or arsenic, and X is hydrogen, fluorine or mixtures thereof.
Preferably further, in said process, said S• deposition is by glow discharge. It is particularly preferred that said deposition is by D.C. glow discharge.
2 Preferably further, in said process, said dopant comprises less than 1% by volume of said deposition gas mixture.
The invention further provides an improved semiconductor device comprising one or more negatively-doped hydrogenated amorphous silicon alloy regions made using one or more dopants having the formula: (SiX 3 )mL X3m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
a0 *Preferably, said semiconductor device is a photovoltaic device.
The invention further provides a method of manufacturing a semiconductor device comprising depositing on a substrate one or more negatively-doped hydrogenated amorphous silicon alloy regions using one or more dopants having the formula: (SiX 3 )m L X3-m 9 -m 3 wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
The invention further provides a semiconductor device comprising one or more hydrogenated amorphous silicon regions wherein at least one of said regions is negatively-doped hydrogenated amorphous silicon alloy made by deposition in a deposition chamber by introducing into the deposition chamber a deposition gas mixture which includes one or more dopants having the formula: (SiX 3 )m L X 3 -m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
Preferably, said semiconductor device is a photovoltaic device.
6 The invention further provides a process for preparing a semiconductor device comprising the step of 4 depositing on a substrate one or more negatively-doped hydrogenated amorphous silicon alloy regions, at least one of said regions being a negatively-doped hydrogenated amorphous silicon alloy made by introducing into a deposition chamber during deposition a deposition gas mixture which includes one or more dopants having the formula:
(SIX
3 L X3m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
The invention further provides a photovoltaic device comprising a front contact, a back contact, and one or more hydrogenated amorphous silicon regions between said front and back contacts wherein at least one of the regions 4 is a negatively-doped hydrogenated amorphous silicon alloy made by deposition in a deposition chamber by introducing into the deposition chamber a deposition gas mixture which includes one or more dopants having the formula: sx. (X 3 )m L X3-m wherein L is a Group 5A atom selected from the group of a 5 phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
The invention further provides a process for preparing a photovoltaic device comprising depositing one or more hydrogenated amorphous silicon alloy regions between a front and back contact wherein at least one or the regions is a negatively-doped hydrogenated amorphous silicon alloy made by deposition in a deposition chamber by introducing into the deposition chamber a deposition gas mixture which includes one or more dopants having the formula: (SiX 3 )m L X 3 wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusiver 6090 I In order that the invention may be further understood, preferred embodiments will hereafter be described by way of the following examples, and with reference to the accompanying drawings, in which:- -6 Figure 1 is an illustration of one embodiment of the present invention wherein a photovoltaic device made in accordance with the present invention includes a p-i-n junction (not to scale).
Figure 2 is a graph plotting the germanium content of hydrogenated amorphous silicon germanium alloy films made by deposition of gas mixtures containing (1) silane and germane and silane and monosilylgermane.
S*
0 99 S
SS**
9 9 o r 7 Figure 3 is a graph plotting the light and dark conductivity as a function of germanium content for hydrogenated amorphous silicon germanium alloy films made by deposition of gas mixtures containing silane and germane and silane and monosilylgermane.
Figure 4 is a graph plotting the quantum efficiency as a function of the light wavelength for a conventional photovoltaic device having hydrogenated amorphous silicon iand n- layers and photovoltaic devices made in accordance with the present invention having hydrogenated amorphous silicon germanium and layers made with monosilylgermane as the germanium source.
Figure 5 is a graph plotting the quantum efficiency as a Panction of the applied voltage at 700 nm for a conventional photovoltaic device having hydrogenated amorphous silicon i- and n- layers and photovoltaic devices made in accordance with the present invention having hydrogenated amorphous silicon germanium i- and n- layers made with monosilylgermane as the germanium source.
20 Figure 6 is a graph plotting resistivity as a function of the optical bandgap for p-layers made in accordance with the present invention using disilylmethane (SiH 3
CH
2 SiH 3 as the source of carbon and conventional p-layers made with iethane (CH 4 as the carbon source.
Figure 7 is a graph plotting the quantum efficiency as a function of the light wavelength for a conventional photovoltaic device having a hydrogenated amorphous silicon carbon alloy p-layer made with methane as the carbon source.
Figure 8 is a graph plotting the quantum efficiency 30 as a function of the light wavelength for a photovoltaic device having a hydrogenated amorphous silicon carbon alloy o* p-layer made in accordance with the present invention with disilylmethane as the carbon source.
Figure 9 is a superimposition of the graphs of Figures 7 and 8.
8 Figure 10 is a plot of the resistivity as a function of the disilylmethane or methane concentration of a conventional p-layer made using methane as the carbon source and a p-layer made in accordance with the present invention using disilylmethane as the carbon source.
Description of the Preferred Embodiments Reference will now be made in detail to the present preferred embodiments of the invention.
A deposition feedstock material for use in the fabrication of hydrogenated amorphous silicon alloys in accordance with the present invention has the following formula:
(MX
3 )nM'X4 wherein M and M' are different Group 4A atoms, at least one of M and M' is silicon, X is hydrogen, halogen or mixtures thereof, and n is an integer between 1 and 4, inclusive.
I. Inclusion of such compounds in the deposition gas mixture during the deposition of a hydrogenated amorphous silicon alloy film onto a substrate in a deposition chamber permits 20 greater control of the incorporation of the Group 4A atoms into the hydrogenated amorphous silicon alloy, thereby reducing the occurrence of undesirable chemical bonds.
The term "hydrogenated" amorphous silicon alloys refers to amorphous silicon alloy which contains at least some *25 hydrogen atoms incorporated in the amorphous silicon alloy.
The term Group 4A atoms refers to atoms of the elements of Group 4A of the Periodic Table, carbon silicon germanium tin (Sn) and lead (Pb).
In the preferred embodiments of the invention, M is silicon and M' is carbon or germanium. The higher the value of n, the more completely the carbon of germanium is surrounded by a matrix of silicon atoms. Surrounding the carbon or germanium with a silicon matrix is desirable because it decreases the likelihood of forming undesirable bonds such 9 as carbon-carbon or germanium-germanium bonds which might otherwise occur. It also reduces the occurrence of undesirable dangling carbon or germanium bonds.
In one preferred embodiment of the invention all of the X atoms are hydrogen Hydroge toms, however, can be replaced in whole or in part with halogen atoms, i.e., fluorine chorine bromine (Br) or iodine In other words, one or more of the X atoms surrounding either the M or the M' atoms can be a halogen atom. Moreover, where more than one X atom is a halogen atom, the multiple halogen atoms can be the same or different halogens.
In another preferred embodiment one or more of the X atoms surrounding either the M or the M' atoms is fluorine.
Good optical and electronic properties have been reported in the literature for fluorinated hydrogenated amorphous silicon alloys. The present invention provides a method of S controlling the manner in which fluorine is incorporated into eve*** the hydrogenated amorphous silicon alloy by including it in the deposition feedstock material of the present invention 20 thereby reducing the likelihood of forming undesirable chemical bonds. Where hydrogen is replaced entirely with fluorine or another halogen in the deposition feedstock material of the present invention, then the deposition gas mixture should preferably include another compound containing hydrogen such as silae (SiH 4 to ensure that there is at least some hydrogen in the resulting alloy.
In accordance with the present invention, if a low optical bandgap hydrogenated amorphous silicon alloy is e: desired, then M' in the above formula for the deposition 0 feedstock material is preferably germanium. In a preferred a low bandgap embodiment of the present invention M is silicon, X is hydrogen, fluorine or mixtures thereof and M' is germanium. Particularly preferred deposition feedstock materials of the present invention useful for forming low bandgap hydrogenated amorphous silicon germanium alloys are: monosilylgermane, SiH 3 GeH 3 disilylgermane (SiH 3 2 GeH 2 trisilylgermane, (SiH 3 3 GeH, tetrasilylgermane (SiH 3 4 Ge, 10 florosilylgermylsilane, FSiH 2 GeH 2 SiH 3 and tetra (trifluorosilyl)germane, (SiF 3 4 Ge. A representative but not exhaustive listing of applications for which low band-gap hydrogenated amorphous silicon alloys are useful include: xerography, laser printers, stacked junction solar cells and in the intrinsic (i-layer) and negatively doped (n-layer) regions of p-i-n type photovoltaic devices.
On the other hand, if a high optical bandgap hydrogenated amorphous silicon alloy is desired, then M' in the above formula for the deposition feedstock material is preferably carbon. In a preferred high bandgap embodiment of the present invention M is silicon, X is hydrogen, fluorine or mixtures thereof and M' is carbon. Particularly preferred deposition feedstock materials of the present invention useful for forming high bandgap hydrogenated amorphous silicon carbon alloy are: monosilylmethane, SiH 3
CH
3 disilylmethane, (SiH 3 2
CH
2 trisilylmethane (SiH 3 3 CH, tetrasilylmethane, (SiH 3 4 C, fluorosilylmethylsilane, .SiH 2
CH
2 SiH 3 and tetra(trifluorosilyl)methane, (SiF 3 4 C. A representative but not exhaustive listing of applications for which high band-gap hydrogenated amorphous silicon alloys are useful include: stacked junction solar cells and the positively-doped (P-layer) regions of p-i-n type photovoltaic devices.
A dopant material for use in the fabrication of negatively-doped hydrogenated amorphous silicon alloys in accordance with the present invention has the following formula: (SiX)mL X 3 m
II
wherein L is a Group 5A atom selected from the group of phosphorous arsenic antimony (Sb) and bismuth (Bi), X is hydrogen, halogen or mixtures thereof, and m i- an integer between 1 and 3, inclusive. Inclusion of such a dopant material in the deposition gas mixture during the deposition of a hydrogenated amorphous silicon alloy film onto a substrate in a deposition chamber permits greater control of 11 the incorporation of the Group 5A atoms into the hydrogenated amorphous silicon alloy, thereby reducing the occurrence of undesirable chemical bonds.
The term Group 5a atom refers to an atom of an element of Group 5A of the Periodic Table.
In the preferred embodiments of the invention, the Group 5A atom is phosphorous or arsenic. The higher the value of m, the more completely the phosphorous or arsenic is surrounded by a matrix of silicon atoms. Surrounding the phosphorous or arsenic with a silicon matrix is desirable because it decreases the likelihood of forming undesirable bonds such as phosphorous-phosphorous or arsenic-arsenic bonds which might otherwise occur. It also reduces the occurrence of undesirable dangling phosphorous or arsenic bonds.
In one preferred embodiment of the invention all of the X atoms are. hydrogen. Hydrogen atoms, however, can be replaced in whole or in part with halogen atoms, i.e., fluorine, chlorine, bromine or iodine. In other words, one or more of the X atoms surrounding either the Si or the Group atoms can be a halogen atom. Moreover, wh-re more than one X V. atom is a halogen atom, the multiple halogen atoms can be the same or different halogens.
In another preferred embodiment of the present invention, one or more of the X atoms surrounding either the Si or Group 5A atoms is fluorine. As explained above, good optical and electronic properties have been reported in the literature for fluorinated hydrogenated amorphous silicon 0 alloys. The present invention provides a method of controlling the manner in which fluorine is incorporated into s 30 the hydrogenated amorphous silicon alloy by including it in the dopant material of the present invention thereby reducing o the likelihood of forming undesirable chemical bonds.
s, In accordance with the present invention, particularly preferred dopant materials fall.ing within formula II which are useful in the fabrication of negatively-doped hydrogenated amorphous silicon alloys are: trisilylphosphine (SiH3) 3 P and trisilylarsine (SiH3)3As. In each of these 12 preferred dopants, the Group 5A atom is completely surround by silicon atoms thereby minimizing the occurrence of undesirable phosphorous-phosphorous, arsenic-arsenic, dangling phosphorous or dangling arsenic bonds.
A dopant material for use in the fabrication of positively-doped hydrogenated amorphous silicon alloys in accordance with the present invention has the following formula:
YJX
2 III wherein Y is halogen or carbonyl, J is a Group 3A atom, and X is hydrogen, halogen or mixtures thereof.
The term "Group 3A atom" refers to an atom of an element of Group 3A of the Periodic Table, boron aluminium gallium indium (In) and thallium (TI).
In accordance with the preferred embodiments of the present invention, the Group 3A atom is boron, aluminium or gallium.
The term "halogen" is defined as above, i.e., S fluorine, chlorine, bromine or iodine. Either one or both X atoms can be halogen. When both X atoms are halogen, they may 20 be the same or different halogens. Likewise when Y and one or both of the X atoms are halogen, the multiple halogen atoms may be the same or different halogens. Preferred dopant materials of formula III wherein Y is a halogen are: boron trifluoride (BF3), boron difluoride (BHF2), aluminium trichloride (AlCl 3 and gallium trichloride (GaC13).
S~ The term carbonyl refers to a carbon and oxygen containing substituent of the formula: -C 0.
A preferred dopant material of formula III wherein Y is carbonyl is borane carbonyl (BH 2
CO).
:30 Use of a formula III dopant material of the present invention, such as boron trifluoride, boron difluoride, aluminium trichloride, gallium trichloride or borane carbonyl, in the deposition of a positively-doped hydrogenated amorphous silicon alloy film on a substrate in a deposition chamber permits greater control of the incorporation of Group 3A atoms into the negatively-doped hydrogenated amorphous silicon 13 alloy, thereby reducing the occurrence of undesirable chemical bonds such as boron-boron, aluminium-aluminium or gallium-gallium bonds.
In accordance with the present invention, hydrogenated amorphous silicon alloy is prepared by of a hydrogenated amorphous silicon alloy film onto a substrate.in a deposition chamber. During deposition, a deposition gas mixture, which includes one or more feedstock materials of the above formula I or one or more dopants of the above formula II or one or more dopants of the above formula III, is introduced into the deposition chamber.
The deposition feedstock materials of the above formula I can be used by themselves, with a dopant material of the present invention (formulas II or III) or with other commonly used deposition feedstock or dopant materials. In accordance with the preferred embodiments of the present invention, the deposition feedstock materials of the present i 0 invention (formula I) comprise between about 1% and 50% by volume of the deposition gas mixture, preferably between about *'20 1% and 20% thereof.
The dopant materials of the above formulas II and III are always used with one or more deposition feedstock materials. The deposition feedstock material with which these dopant materials are used can be either deposition feedstock materials of the present invention or other commonly used deposition feedstock materials or combinations thereof. In accordance with the preferred embodiments of the present invention, the dopant materials of the present invention (formulas II or III) comprise between about 0.000001% and 30 by volume of the deposition gas mixture, preferably between about 0.001% and 1.0% thereof.
A representative but non-exhaustive list of other deposition feedstock and dopant materials that can be used with the deposition feedstock or dopant materials of the present invention include silane (SiH 4 higher silanes such as disilane (Si 2
H
6 and trisilane (Si 3
H
8 germane (GeH 4 higher germanes such as digermane (Ge 2 H ammonia (NH 3 14 hydrogen (H 2 methane (CH 4 phosphine (PH 3 arsine (AsH 3 diborane (B 2
H
6 fluorine (F 2 arsenic pentafluoride (AsF 5 nitrogen trifluoride (NF 3 phosphorus pentafluoride (PF 5 and phosphorus trifluoride (PF3).
Silane is a preferred additional deposition feedstock material for use with the deposition feedstock and/or dopant materials of the present invention because it is readily available in the relatively pure form which is necessary for semiconductor manufacture. While the present invention can be practiced with some contaminants, it is preferable to use deposition feedstock and dopant materials which are as pure as possible.
In a preferred embodiment of this invention, deposition is accomplished using a conventional glow discharge technique, such as D.C. glow discharge, R.F. glow discharge, A.C. glow discharge or microwave glow discharge. See, e.g., U.S. Patent No. 4,064,521, the disclosure of which is incorporated by reference herein. Preferably, the deposition substrate temperature is between about 1500 and 400 0 C, more 0, preferably between about 2200 and 260 0 C, Preferably, the deposition pressure is between about
S
e* 0O 0 0 15 0.1 and 10 torr, more preferably between about 0.5 and 1.0 torr.
SPreferably, the cathode current density is between about .01 and ma/cm 2 more preferably between about 0.1 and 0.3 ma/cm 2 Alternatively, other conventional deposition techniques can be used. These other deposition techniques include: chemical vapor deposition, photochemical vapor deposition, low pressure chemical vapor deposition, homogeneous chemical vapor deposition, sputtering and reactive sputtering in the presence of hydrogen.
Deposition of the hydrogenated amorphous silicon alloy film as described above can be promoted by activation of the deposition feedstock materials of the present invention by dehydrogenation or dehalogenation. Dehydrogenation or dehalogenation of the deposition feedstock materials of the present invention will lead to the formation of activated molecules or radical's that can readily bond to the surface of a growing film.
The activation of the deposition feedstock materials of the S present invention can be accomplished by photochemical vapor deposition. This technique may be used to selectively break Si-H bonds without breaking other molecular bonds. This may be cg.9* accomplished by conventional single or multi-photon processes and can also be accomplished by using conventional activated intermediates such as mercury (Hg).
Activation of the deposition feedstock materials of the i present invention can also be accomplished by reaction with OffiCES 1. HENDERSj N w. CARRETT tUNNER.
STRrLT.N.W.
)H.D.C.Zooo so 16 atomic hydrogen. Atomic hydrogen may be generated in a separate chamber by a plasma, hot filaments or catalytic activity in a conventionally known means and then injected into the deposition chamber containing the silyl compounds. This approach may relquire the use of gas flow isolation of the atomic hydrogen generiation chamber to prevent the deposition feedstock materials of Ithe present invention from diffusing into the generation chamber.
Activation of the deposition feedstock materials of the ;present invention can also be accomplished by catalytic dehydro- :genation or dehalogenation in a conventionally known manner. For example, certain compounds or elements such as platinum (Pt) and palladium (Pd) are able to catalytically dehydrogenate certain ihydrogen containing compounds.
Activation of the deposition feedstock materials of the
I
'present invention via dehydrogenation can also be accomplished ,via conventionally known reactions with molecular or atomic fluorine. That is, fluorine will react with some hydrogen-containing compounds to remove the hydrogen and form HF molecules.
Activation of the deposition feedstock materials of the 0* present invention can also be accomplished via energetic electrons. The deposition system can be configured so that monoo I energetic electrons are injected into the deposition atmosphere.
S* The injection energy should be selected so that there is a high probability of breaking Si-H bonds or Si-halogen bonds and a low '!probability of breaking other bonds.
rrccn HENDERSON
GARRETT
INNER
i 17 S The above methods of activating the deposition feedstock materials of the present invention via dehydrogenation or dehalogenation will be applicable even if the deposition contains inert !igases such as argon (Ar) or other deposition gases such as silane l(SiH 4 disilane (Si 2
H
6 or hydrogen (H 2 To promote dehydrogenation or dehalogenation the substrate is preferably heated to a temperature in the range of 150 to 4000C.
In a preferred embodiment of the present invention, activation of the deposition feedstock and dopant materials is 0 accomplished by using mercury-sensitized photochemical vapor dep- I osition. Preferably, deposition is carried out with a substrate temperature of between about 150 and 400°C, more preferably between about 220 and 260°C. The deposition pressure is preferably between about 0.1 and 50.0 torr, more preferably between about 1.0 and 10.0 torr. Before being introduced into the reac- 'tor, the deposition feedstock and dopant materials are diluted with hydrogen and pre-mixed with a very small amount.of mercury vapor in a thermally controlled conventional mercury vaporizer.
Ultraviolet light from a conventional low pressure mercury lamp 0 is transmitted through a transparent window placed between the S' mercury lamp and the substrate. The ultraviolet light energy fom the mercury lamp excites the mercury atoms which then activates the deposition feedstock and dopant materials by dehydrogenation or dehalogenation.
HENDERSON
CARRETT
NNER
CCT. c .W.
.o.c.Zoo0 -oso 18 i In accordance with the present invention, the hydrogenated amorphous silicon alloy film can be deposited on any suitable substrate. A representative but not exhaustive list of substrates suitable for use in practicing the present invention include conducting transparent oxides and stainless steel.
An improved semiconductor device made in accordance with the present invention comprises one or more hydrogenated amorphous silicon alloy regions made from either one or more feedstock materials of the above formula I, or one or more dopants of the above formula II or one or more dopants of the above formula III. Such a semiconductor device is prepared by depositing on a substrate, preferably by a glow discharge or a photochemical vapour deposition process, one or more hydrogenated amorphous silicon alloy regions at least one of the regions being made by introducing into the deposition chamber during deposition a deposition gas mixture which includes either one or more feedstock materials of the above formula I, one or more dopants of the above formula II or one 20 or more dopants of the above formula III. A representative but not exhaustive list of types of semiconductor devices which can be made in accordance with the present invention includes: photovoltaic devices, current rectifying devices, photodetectors, thin film resistors, and photoreceptors. As 25 embodied herein, the preferred semiconductor device made in accordance with the present invention is a photovoltaic device.
A photovoltaic device in accordance with the present invention comprises a front contact, a back contact and one or 30 more hydrogenated amorphous silicon regions between the front and back contacts, wherein at least one of the regior, is a hydrogenated amorphous silicon alloy made by deposition, preferably by a flow discharge or a photochemical vapour deposition process, in a deposition chamber by introducing into the deposition chamber a deposition gas mixture which 19includes either one or more feedstock materials of the above formula I, or one or more dopants of the above formula II, or one or more dopants of the above formula III.
The term front contact refers to the contact on the light incident side of the photovoltaic device. The term back contact refers to the contact on the side opposite the light incident side of the photovoltaic device.
One embodiment of the present invention is illustrated in Figure 1 (not to scale). As shown in Figure 1, light enters the light incident sid of a photovoltaic cell. The light passes first through a glass layer then through a transparent conductive layer which serves as a front contact, and then into the hydrogenated amorphous silicon region Lastly, on the side opposite the light incident side of the photovoltaic device is a metal back contact *oof* *In Figure 1 the hydrogenated amorphous silicon region is a p-i-n junction. That is, the iydrogenated amorphous silicon region includes a positively doped layer *o 20 (p-layer) an intrinsic layer (i-layer) and a *55 S negatively doped layer (n-layer) N conventional hydrogenated amorphous silicon photovoltaic cell having a p-i-n junction of this same general form is shown, for example, in United States Patent No. 4,217,148, the disclosure 25 of which is incorporated by reference herein.
obso Alternatively, the hydrogenated amorphous silicon 0 0 regions could take the form of other conventional Ssemiconductor diode arrangements. A representative but not exhaustive list of other arrangements include: *30 p-layer/n-layer; n-layer/i-layer/p-layer; and n-layer/p-layer.
These arrangements, as well as Schottky barriers and stacked junctions can also form the hydrogenated amorphous silicon region in a photovoltaic cell such as shown in Fig. 1.
The present invention is also particularly suitable for photovoltaic devices wherein the hydrogenated amorphous silicon region has a graded optical bandgap. By use of the deposition feedstock materials of the present invention, Group 20 4A atoms other than silicon can be incorporated into the hydrogenated amorphous silicon alloy. As explained above, these Group 4A atoms will affect the bandgap of the resulting hydrogenated amorphous silicon alloy layers. Thus, by using different deposition feedstock materials of the present invention in the deposition gas mixtures used to form different layers in the hydrogenated amorphous silicon region, a graded bandgap structure can be obtained.
The deposition feeds.cock materials of the present invention as set forth in formula I above can be synthesized by a number of different methods. One method of synthesizing these compounds is in a silent electric discharge (sometimes referred to as an ozonizer type of electric discharge).
Several researchers have prepared silylgermanes in small (mg) quantities by the action of a silent electric discharge upon a mixture of silane and germane. See T.D.
Andrews and C.S.G. Phillips. "Further Studies on the Silicon-Germanium Hydrides," J. CHEM. SOC (1966) pp.
46-48; S.D. Gokhale, J.E. Drake anu W.L. Jolly, "Synthesis of 20 the Higher Silanes and Germanes,: J. INORG. NUCL. CHEM. (1965) S Vo. 27, pp. 1911-1916; E.J. Spanier and A.G. MacDiarmid, "The S Synthesis of Germylsilane from Silane and Germane in a Silent Electric Discharge,: INORG. CHEM. (1963) Vol. 2, pp. 215-216.
Example 1 describes a similar, but scaled up, 25 technique which was used to prepare several grams of monosilylgermane: S Example 1 SApproximately five grams of AircoOCCD grade silane and six grams of Matheson germane were introduced into a 30 conventional silent electric discharge reactor having a volume S of 8.4 1. and a pressure of 525 torr. A conventional metal bellows pump recirculated the gas mixture through the reactor for three hours. A conventional cold trap kept at -90 0 C by flowing nitrogen gas cooled by liquid nitrogen, trapped the silylgermanes while passing the unreacted silane and germane and the hydrogen product. The silane, germane, and hydrogen 21 were pumped away and the coLlected, impure silylgermanes were distilled through a conventional cryogenic distillation column to purify the monosilylgermane. The purified monosilylgermane was analyzed using a conventional gas chromatograph-mass spectrometer. The only major impurity ir the monosilylgermane was disilane at a level of 100 ppm. All other higher order silanes, germanes, and silylgermanes were reduced to levels less than 1 ppmw. Occasionally, digermane was observed in some purified monosilylgermane samples at levelsof 1-5 ppmw.
After purification, the monosilylgermane was stored in a stainless steel cylinder.
Another suitable method for preparing deposition feedstock materials of the present invention is described in copending United States patent application Serial No. of Benjamin Frederick Fieselman, entitled "Preparation of Silicon and Germanium Il-' ides containing Two Different Group 4A atoms," filed concurrently herewith, the disclosure of which is incorporated herein. This patent application discloses a method for preparing a hydride containing at least two different Group 4A atoms, wherein at least one of the Group 4A atoms is silicon or germanium. First, a salt comprising a cation potassium) coordinated to a microcyclic compound a crown ether such as 18-crown-6) and an anion a silicon hydride such as SiH3- or a germanium hydride such as GeH 3 is formed in a suitable solvent distilled monoglyme). This salt is then reacted with a Group 4A halide SiH 3 Cl, CH 3 I or CH 2 C12). This patent application specifically reports the preparation of monosilylgermane, SiH3GeH 3 monosilylmethane, SiH 3
CH
3 and disilylmethane, 30 (SiH 3 2
CH
2 Other deposition feedstock materials of the present invention can be made by this same process by employing different Group 4A halides or hydrides.
Another suitable method for preparing deposition feedstock materials of the present invention is the acid hydrolysis of an alloy of magnesium, silicon and a Group 4A element other than silicon. See, P.L. Timms, C.C.
Simpson, and C.S.G. Phillips, "The Silicon-Germanium 22 Hydrides", J. CHEM. SOC. (1964) 1467-1475 (Timms et al.); C.S.G. Phillips and P.L. Timms, "Some Applications of Gas Chromatography in Inorganic Chemistry," J. ANAL. CHEM. (April 1963) Vol. 35 No. 4, pp. 505-510. The following example reported in Timms et al. illustrates the preparation of certain feedstock materials suitable for use in the present invention by the acid hydrolysis of an alloy of magnesium, silicon and another Group 4A element (in this case germanium): Example 2 2 g of an alloy of nominal composition MG 20 Si 9 Ge was tamped into five 1 cm. x 1 cm. thin-walled aluminium-foil cylinders. During 15 min., the cylinders were added one by one to 200 ml. of hydrofluoric acid (10% w/w) in a polythene flask (1 where the foil dissolved quickly, releasing the alloy into the acid. Hydrogen was bubbled at 600 ml./min.
into the flask to carry the hydrides through a drying tube, containing phosphorus pentoxide (ca.20 and into a trap cooled by liquid oxygen. The hydrogen was maintained for min. after the addition of the alloy. A blow-off, operating 20 at 12 cm of mercury, avoided excessive pressures in the reaction flask, and the flushing hydrogen emerged into the atmosphere through a mercury bubbler and was burnt. The bulk of the monisilane and monogermane in the 150-200 mg. of hydrides formed was normally removed by warming the trap to 25 The residual higher hydrides were then carried in a stream of hydrogen to one of the traps immediately before the g.l.c. columns.
The deposition feedstock materials of the present invention can also be made by pyrolysis. The following 30 example reported in Timms et al. illustrates the preparation of certain deposition feedstock materials suitable for use in the present invention by the pyrolysis of a germane with a silane: S23 Example 3 Hydrides were thermally cracked at 290-3500 to give mainly simpler volatile fragments. Once cracker was a Pyrex tube (5 cm. x 4 mm.) packed with glass wool and heated electrically. Hydrides were passed through the tube in hydrogen or nitrogen streams with a residence time of about 1 sec., and volatile materials were trapped and then separated on a g.l.c. column (5 ft. x 3 mm.) packed with 10% Silicone 702 on Celite operated at room temperature. Reproducible "cracking patterns" were obtained with samples larger than about 30 ug. Silicon-germanium hydrides were formed, by condensing a silane with a germane of similar boiling point in a trap before an 8 cm. x 1 cm. Pyrex tube, which was packed with glass wool and heated to 350-3700. The hydrides were evaporated quickly from the trap to pass through the tube with a residence time of 0.3-0.6 sec. in a hydrogen stream, the products being trapped and separated by g.l.c.
Sof,, Another method of synthesizing deposition feedstock materials suitable for use in the present invention is described in J.A. Morrison and J.M. Bellama, "Synthesis and Characterization of the (Halosilyl) methyls-ilanes", J.
ORGANOMETALLIC CHEMISTRY, 92 (1975) pp. 163-168 (Morrison et al.).
Example 4 describes a scaled up version of Morrison 25 et al.'s technique which was used to prepare several grams of S disilylmethane: Example 4 93.3 gm of Aldrich Gold Labelo tri-n-butyl amine, a 29.1 gm of chloroform (CHCl 3 distilled and dried free of 30 ethanol and 165 gm of Petrarch ®SiHCl 3 were mixed and stirred 3 S for one hour without heating. The mixture was then refluxed with cooling in a 500 ml. flask with a conventional CaC12 drying tube attached. After about one hour heat was added to keep the mixture at a constant reflux. The temperature of the reflux rose from 30°C to 45 0 C. The mixture was refluxed for a total of 12 hours. The CaC12 drying tube was replaced with a 24 conventional N 2 bubbler so that when the system cooled it filled with nitrogen. The mixture was allowed to cool overnight. The mixture was then decanted twice with heptane at -7 C to -8 C. The heptane was removed at -10 C with a conventional rotary evacuator. The residue was dissolved in 150-200 ml of Aldrich Gold Label n-dibutyl ether under N 2 Then LiAlH 4 was added slowly over 102 hours. Product was continuously separated under vacuum.
Morrison et al. also describe the preparation of chloro-, bromo-, and iodosilyl) methylsilanes, i.e., CISiH 2
CH
2 SiH 3 BrSiH 2
CH
2 SiH 3 and FSiH 2
CH
2 SiH 3 Example 5 is taken from Morrison et al.: Example A small amount of the appropriate aluminium halide was sublimed onto the walls of a one liter vessel.
Disilylmethane and hydrogen halide in a 3/1 molar ratio were vacuum distilled into the vessel, and the reagents were allowed to react at room temperature for one hour. The contents of the flask were then distilled. Hydrogen was 20 removed, and material which passed a -95 trap (unreacted (SiH3)2CH 2 and a small amount of HX where X is a halogen) was returned to the reaction vessel with enough HX to reconstitute a 3/1 molar ratio. This process was repeated until most of the disilylmethane had been consumed. The combined S 25 condensates from the -950 trap were then distilled from a lower temperature still.
s Morrison et al. also describe the preparation of fluoroxilyl methylsilane, FsiH 2
CH
2 SiH 3 Example 6 is taken from Morrison et al: Example 6 Fluorosilylmethylsilane was prepared by the reaction of bromosilylmethylsilane with lead (II) fluoride. Two grams of freshly prepared PbF 2 and a stirring bar were placed into a 200 ml flask which was then evacuated.
Bromosilylmethylsilane, 0.95 g (6.1 mmol) was distilled into 25 the vessel and allowed to react at room temperature. After two hours the volatile contents of the flask were condensed into a low temperature still from which 0.30 g FSiH 2
CH
2 SiH 3 (3.2 mm 51% yield) was collected at -109 C.
Another method of synthesizing deposition feedstock materials of the present invention is described in R.A.
Benkeser, J.M. Gaul and W.E. Smith, "Silylation of Organic Halides. A New Method of Forming the Carbon-Silicon Bond," J.
AMERICAN CHEMICAL SOCIETY, 91:13, June 18, 1969, pp. 3666-7 (Benkeser et Example 7, taken from Benkeser et al., describes the preparation of hexachlorodisilylmethane (SiCl3)2CH 2 Example 7 A mixture of 1 mole of chloroform, CHC13, 4.5 moles of trichorosilane, SiHCl 3 and 3 moles of tri-n-propylamine were refluxed at 56-65 C for 16 hours in the presence of CH 3
CN
S. to form hexachlorodiilylmethane, (SiC 3 2
CH
2 Example 8 illustrates hydrogenated amorphous silicon alloy films made in accordance with the present invention *20 using monosilylgermane as a deposition feedstock material: 0r Example 8 Hydrogenated amorphous silicon germanium alloy films were prepared using a conventional DC proximity glow discharge S deposition system and a deposition gas mixture which included 25 the monosilylgermane synthesized by the method disclosed in Example 1. Typically, the best films were prepared at a substrate temperature of 220 C, a total gas pressure of S2o torr, and a cathode current density of 0.09 ma/cm2. To change the germanium content in the deposited films, the flow rate of 30 monosilylgermane was varied from 0 to 50 standard cubic La *l
S
a centimeters per minute (SCCM). Silane was simultaneously added to make the total flow rate 100 SCCM during the deposition.
To determine the germanium content in the silicon germanium films, a relative atomic ratio was measured with an electron microprobe technique using an ISI super III SEM and a 26 KEVEX Model 5100 X-ray spectrometer. Figure 2 compares the incorporation rate of germanium in the silicon germanium alloys prepared from monosilylcrmanium and germane each mixed with various amounts of silane. The curve is parabolic for both, indicating a similar germanium incorporation mechanism.
However, less germanium is incorporated into the solid films for a given mole fraction of germanium feedstock in the gas phase when monosilylgermane was used. This is an expected result because more silicon atoms are present in a gas chase mixture of monosilylgermane and silane than for an equivalent silane and germane mixture.
To characterize the hydrogenated amorphous silicon germanium alloys, thin films 3000 A thick were prepared with various amounts of monosilylgermane and silane. Samples for optical measurements were deposited on quartz substrates, while samples for conductivity measurements were deposited on quartz substrates having chrome strips for four point probe *s measurements.
The optical band gaps were determined from optical 20 absorption measurements using the Tauc relation oC hY"= C(hV 2 S-E where E in eV is the optical bandgap, C is the Tauc coefficient in um eV h Y is the absorbing photon energy in -1 eV, and oC is the absorption coefficient in pm Light (AM1) and dark conductivity were determined by a high impedance four point probe DC measurement.
Figure 3 plots the light and dark conductivity as a function of the germanium content (x in Si lxGex) in the solid film for alloys made from mixtures of silane and monosilylgermane and for alloys made from mixtures of silane 30 and germane. The dark current (low 10- 1 0 J -cm 1 as a function of x is nearly the same for both hydrogenated aOme amorphous silicon germanium alloys indicating good 6u 1' semiconductor electrical properties. However, the light conductivity decreases quickly as the germanium content increases in the hydrogenated amorphous silicon germanium alloys made from silane and germane. For bandgaps smaller than 1.6eV the photoconductivity of the hydrogenated amorphous 27 silicon germanium alloys muade using monosilylgermane and silane is an order of magnitude better than the hydrogenated amorphous silicon germanium alloys made using silane and germane. This is important because the better the photoconductivity the better the transport properties of the solar cell.
sea 966 .0 00 5e00 28 The superiority of silicon germanium alloys made from monosilylqermane as illustrated in Figure 3 is likely due to a reduction in dangling bonds on germanium. Using monosilylgermane one silicon atom is chemically bonded to the germanium atom prior to deposition. It is well known that many species are formed in a Isilane (and germane) glow discharge. However, the probability of forming SiH 3 GeH 2 groups is greater than GeH 3 GeH2- groups because the Ge-H bond is weaker than the Si-H bond and because the germyl group is larger than the silyl group. This means a reduction (but not an elimination) of germanium dangling bonds. Similarly, it is expected that H 2 Ge- and Ge-Ge bonds would be minimized in 'the solid film if disilylgermane, (SiH 3 2 GeH2, trisilylgermane, i(SiH 3 3 GeH, or tetrasilylgermane, (SiH 3 4 Ge, were used as deposition feedstock materials in, the deposition ga,; mixture to deposit silicon germanium alloys. In this way, germanium dangling bonds would be reduced or eliminated and superior hydrogenated amoriphous silicon germanium alloys formed.
Example 9 illustrates photovoltaic devices made in accor- 0 ;,dance with the present invention.
Example 9 p-i-n type photovoltaic devices such as is illustrated in SFigure 1, were fabricated using the hydrogenated amorphous silii con germanium alloy films prepared by the method disclosed in Example 8.
iE14DERSO
CARREWT
4NER ICC I N.W.
0. Z00 3-0430 t 29 The control cell for comparison in these experiments consisted of an a-SiC:H p-layer 100 A thick, a 5200 A thick i-layer 0 of a-Si:H, and a 500 A thick a-Si:H n-layer.
The test cells had a structure consisting of an a-SiC:H O 0 p-layer 100 A thick, a 2500 A thick i-layer of a-Si:H, a 2500 A Sthick i-layer of a-SiGe:H and a 500 A thick a-SiGe:H n-layer.
Both the 2500 A thick a-SiGe:H i-layer and the 500 A thick a-SiGe:H n-layer were made by the method disclosed in example 8 using monosilylgermane (prepared in Example 1) and silane in the LO deposition gas mixture.
I The substrate temperature was 240*C during deposition for s* the control cell. The hydrogenated amorphous silicon germanium alloys were deposited at a substrate temperature of 220"C.
All solar cells were deposited on 10J1/G conductive fluroinated tin oxide (CTO) front contact substrates. The p-i-n 0 0 diodes were completed with a 20 A /Ti and 3500 A Ag back contact Smetallization. Individual small test cells having areas of 0.3cm 2 were defined by a mask during metal deposition. The sub- *.strate temperature for test cells was 240°C except during the- 0 deposition of the Si-Ge alloys where the substrate temperature lowered to 22 0
°C.
i The characteristics of the fabricated solar cells are summarized in Table I. The measurements were made using AM1.5 illumi- !nation at 100mW/cm 2 IENDER0SN
CARRAETT
INER
Cl H.W.
O.C. 0000 -e*O N L* 0 Vrn *00 0 S S
S
1. 3 0 5 0
S
0*
S
@00 000
S
500 S *0 *0 0 0
SOS
00 0 SO 005 @0 550 S 5 0 S 50 05 0 0* 0 0 @0 060 0 a 0@0 0 0 0 0 005 TABLE I Characteristics of Amorphous Silicon Germanium Solar Cells Fabricated With Monosilylgermane Efficiency in Short Open Deposition Gas Bandgap of Converting Solar Circuit Circuit Collection Mixture Used Solid Phase Energy to Current Voltage Length in Preparation Composition Electrical Fill Jsc Voc Lc/L at of i-layer of i-layer Energy W% Factor (ma/cm 2 700 nm SiH-4 1.72eV a-Si:H 10.24 0.759 15.73 0.857 1.72ev a-Si:H/ SiH3GeH3 1.59eV a-SiGe:H 9.53 0.700 15.99 0.852 14 SiH4 1.72ev a-Si:H/ SiH3GeH3 1.52eV a-SiGe:H 7.25 0.604 15.24 0.782 4 SiH4 The fill factor of the tested solar cells decreases with increasing incorporation of germanium into the i-layer.
Device fabrication produced solar cells having an efficiency of 9.53% for a hydrogenated amorphous silicon germanium alloy having Eg.(bandgap)= 1.59eV and 7.25% for a hydrogenated amorphous silicon germanium alloy having Eg 1.52eV.
Figure 4 shows the quantum efficiency as a function of the light wavelength of the fabricated solar cells listed in Table I. The data used to plot figure 4 is reported in Table II: TABLE II Quantum Efficiency 020 g oe *.s se '20 *o
S
(nm) 1.72ev a-Si:H 1.59ev a-SiGe:H 1.52ev a-SiGe:H 600 0.726 0.742 0.705 620 0.687 0.714 0.642 640 0.609 0.648 0.564 660 0.506 0.563 0.472 680 0.387 0.452 0.381 700 0.285 0.345 0.321 720 0.168 0.219 0.231 740 0.074 0.108 0.132 760 0.032 0.054 0.071 780 0.015 0.025 0.038 800 0.006 0.011 0.018 The solar cell fabricated with 1.59eV a-SiGe:H alloy showed an improved red response with no effect on the blue response of the solar cell when compared to the control. This is also observed as a slight increase in the short circuit current J However, the solar cell fabricated with a 1.52eV sc a-SiGe:H alloy showed a slight increase in the red response 32 but an overall decrease in the blue and mid-bandgap absorption regions. This is reflected in the cell performance by a decrease in the short circuit current.
it is also observed in Table I that the fill factor decreases with increasing germanium incorporation. An excellent fill factor of 0.70 was measured for the cell fabricated with 1.59eV a-SiGe:H alloy. However, for the solar cell'fabricated with a 1.52eV a-SiGe:H alloy the fill factor decreased to value of 0.60 which is satisfactory. The fill factors are decreasing because of the deterioration of the material transport properties with increasing germanium incorporation into the deposited alloy films.
The quantum efficiency as a function of the applied voltage at 700nm for the solar cells listed in Table I under reverse bias conditions is displayed in Figure 5. It is observed in this figure that all of the carriers generated at a reverse bias of -2.0v.are collected at 0.Ov bias condition (normal solar cell operation) for the control cell and for the S1.59eV a-SiGe:H alloy solar cell. However, not all the charge 20 carriers produced under -2.0V reverse bias conditions are collected under 0.OV bias conditions for the 1.52eV a-SiGe:H alloy solar cell. This results in a dramatic decrease in collection length from c /L value of 24 to an 1 c /L value of 4 at 400nm. Hence, there is a corresponding reduction in fill factor.
Example 10 illustrates the superiority of hydrogenated amorphous silicon alloy films made in accordance with the present invention using disilylmethane as a deposition feedstock material.
Example i* Hydrogenated amorphous silicon carbon alloy p-layers were prepared using a conventional DC proximity glow discharge deposition system. The p-layers were deposited on 1/2" x 3" quartz slides upon which chrome stripes had been previously evaporated. The chrome stripes were used to make electrical 33 contact with four point DC conductivity (resistivity) test apparatus. Generally, the thickness of the films were 2000-4000 A thick.
for the control (comparison) p-layers, the deposition gas mixture included either methane (CH silane (SiH4), and diborane (B 2 Hg) or just silanie and diborane.
For the p-layers made in accordance with the present invention, the deposition gas mixture included disilylmethane, (SiH 3 2
CH
2 (synthesized by the method disclosed in Example silane and diborane.
The flow rates of these deposition gases were varied to change the carbon contents in the deposited p-layers.
Total flow rate was kept at 100 SCCM and the amount of diborane was kept constant at 1.83 x 10 3 parts by volume of the total deposition gas mixture. The p-layers were prepared at a substrate temperature of about 220 0 C, a total gas pressure of 0.5 torr, and a cathode current density of.
0.14 ma/cm The time of deposition was altered to 2 accommodate variations in deposition rate so that the 20 resulting p-layers were within the 2000-4000 A range.
Table III summarizes the results obtained from measuring the resulting p-layers. Bandgaps were measured using the Tauc relation o< hV=C(h 7 -E 2 and optical absorption measurements.
O.
C
O0 a 34 TABLE III Run Composition of Bandgap Resistivity Deposition Gas Eg (e v) Mixture 2 3 4 Bse..
20
S
9 f 12 SCCM 1 1/2% B2H 6 in SiH 4 8" SCCM SiH 4 3 SCCM (SiH 3 2
CH
2 12 SCCM 1 1/2% B 2
H
6 in SiH 4 SCCM SiH 4 5 SCCM (SiH 3
)CH
2 12 SCCM 1 1/2% B2H 6 ir SiH 4 83 SCCM SiH 4 6 SCCM (SiH 3 2
CH
2 12 SCCM 1 1/2% B 2
H
6 in SiH 4 82 SCCM SiH 4 9 SCCM (SiH 3 2
CH
2 12 SCCM 1 1/2% B2H 6 in SiH 4 79 SCCM SiH 4 12 SCCM 1 1/2% B 2
H
6 in SiH 4 88 SCCM SiH 4 SCCM CH 4 12 SCCM 1 1/2% B 2
H
6 in SiH 4 63 SCCM SiH 4 4 50 SCCM CH 4 12 SCCM 1 1/2% B2H 6 in SiH 4 38 SCCM SiH.
1.89 1.96 2.04 2.09 2.13 1.89 1.99 2.15 1.94 x 105 1.55 x 10 4.83 x 10 1.51 x 10 6 4.48 x 10 6 1.85 x 10 1.64 x 10 2.04 x 2.04 x c 0 5
S
The bandgap for the hydrogenated amorphous silicon film containing no carbon was 1.89 eV. Usually, however, the bandgap for such films are 1.72 eV. The higher bandgaps were obtained in this example because the deposition occurred at about 2200C instead of the preferred temperature of 2400C.
Thus, the resistivities measured from the p-layers made in this example are approximately a factor of ten times higher than they would have been had the preferred 240 C deposition temperature been used.
Figure 6 plots the resistivity as a function if bandgap for the p-layers summarized in Table III. Figure 6 illustrates that p-layers made in accordance with the teachings of the present invention using disilylmethane as the carbon source have lower resistivities for a given bandgap than p-layers made with methane as the carbon source.
Example 11 illustrates the superiority of photovoltaic devices made in accordance with the present invention wh-rein disilylmethane is used as a deposition feedstock material in the deposition gas mixture to form the p-layer of the photovoltaic device.
Example 11 P-i-n type photovoltaic devices, including a control 0 device and test devices made in accordance with the present tt invention, were fabricated with a hydrogenated amorphous 0 0 silicon carbon p-layer approximately 100 A thick.
a.
20 The p-layers were deposited in a D.C. glow discharge e2 using a cathode current density of 0.14 ma/cm a substrate temperature of 220 0 C, and a total gas pressure of 0.5 torr.
In the control device, the deposition gas mixture for forming the p-layer was 50 SCCM CH 4 12 SCCM 1-1/2% B 2
H
6 25 in SiH 4 and 38 SCCM SiH 4 In the test devices made in accordance with the present invention, the deposition gas mixture for forming the p-layer was 9 SCCM (SiH 3 2
CH
2 12 SCCM 1-1/2% B 2
H
6 in SiH 4 and 79 SCCM SiH S 4 o Both devices had similar 5200 A hydrogenated amorphous silicon i-layers deposited in the D.C. glow discharge using a cathode current density of 0.14 ma/cm a substrate temperature of 220 0 C, a i.otal gas pressure of torr. and a flow rate of 120 SCCM SiH 4 36 Both devices had similar 500 A hydrogenated amorphous silicon n-layers deposited in the D.C. glow 2 discharge using a cathode current density of 0.12 ma/cm 2 a substrate temperature of 220 0 a total gas pressure of torr, and a flow rate of 12 SCCM 4% PH 3 in SiH 4 and 88 SCCM SiH 4 4' o Both devices had similar 20 A Ti/3500 A Ag back contacts, and similar 10t/L conductive transparent oxide fluroinated tin oxide) front contacts.
Figure 7 plots the quantum efficiency as a function of the light svaw.vlength for the control device wherein methane is used as the carbon source for fabricating the p-layer.
Figure 8 plots the quantum efficiency as a function of the light wavelength for the best test device made in accordance with the present invention using disilylmethane as the carbon source. The data used to plot figures 7 and 8 is reported in Table IV: 0e 6 go* 0.
*1 0 "*llr 37 .0 0-4IZOO I *eas TABLE IV Quantum Efficiency 2.13eV a-SiCifl (SiH3)2CH2 used as carbon source b light wavelength (nm) 2.15eV a-SiCiH C~l used as carbon source 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760 780 800 0.653 0.711 0.743 0.789 0.815 0.837 0.839 0.848 0.852 0.815 0.765 0.702 0.646 0.562 0.441 0.311 0.198 0.091 0.038 0.013 0.003 0.491 0.563 0.618 0.684 0.742 0,746 0.762 0.788 0.798 0.764 0.722 0 .657 0. 590 0 .507 0.387 0.252 0 .150 0.041 0.016 0.006 0.001 -38 Figure 9 superimposes the plots of figures 7 and 8.
As is illustrated therein, the quantum efficiency of the solar cell at a light wavelength of 400 nm increases from less than efficient for the control solar cell made with methane as the carbon source to greater than 65% efficient for the solar cell made in accordance with the present invention using disilylmethane as the carbon source. This is a substantial improvement in the blue response of the solar cell.
Table V reports other data measured for the control and test solar devices of Example II. This data illustrates the superiority of solar cells made in accordance with the present invention using disilylmethane as the source of carbon in the deposition gas mixture.
S
o*
~J
see
O
cb o 9S
S*
OO
*I 39 0 o' a a a S a a. *a a a a a a a a a a a 0 a S OS a S S a 0 S a.
S 555 .00 00 a S. a a a a *a a. S *0 a SO 0 a a a a a a a a aa.
Deposition Efficiency in Short Open Feeds tock Converting Solar Circuit Circuit Materia3s Used Bandgap of Energy to Current Voltage To Form a.-SiC:H Electrical Fill Jsc Voc p-layer* p-layer Energy W% Factor (ma/cnfi 2 (v)
CONTROL
4 2.15 9.09 0.727 15.06 0.829 4 RUN #1 8.9%SiH 3
CH
2 SiH 3 2.13 9.32 0.700 16.61 0.802 91.1% SiH 4 RUN #2 8.9%SiH 3
CH
2 SiH3 2.13 9.92 0.742 15.76 0.848 91.1% SiH 4 *Deposition gas mixture also included 0.18% of B 2
H
6 Very little disilylmethane is required to open the bandgap of a p-layer in a p-i-n type solar cell. This is illustrated in Figure 10 which is a plot of the resistivity as a function of the disilylmethane or methane concentration in the p-layers of the control and test solar cells of Example II. Resistivity increases with increased carbon incorporation. Thus, disilylmethane is a highly efficient source of carbon for incorporation thereof in the hydrogenated amorphous silicon carbon alloy p-layer of a p-i-n type solar cell device.
The dopant materials of the present invention as set forth in formulas II and III above can be synthesized by a number of different methods. The following example reported in E. Amberger and H. Boeters, "Preparation and Properties of 15 Trisilylarsine" Angew. Chem. Int. Ed. 1, 268 (1962) illustrates the preparation of a preferred dopant of formula II, trisilylarsine, (SiH3)3As: Example 12 Trisilylarsine is formed in 48% yield by the reaction of monobromosilane (SiH 3 Br) with potassium arsinedihydride KAsH 2 in a 1:1 molar ratio. In this preparation, the two reactants are allowed to warm up slowly together in the previously frozen reaction medium, dimethyl ether. The reaction begins at -122 C and is completed at -38 0 C after 2 hours. Arsine, ether and unreacted silyl bromide are separated from trisilylarsine by vacuum distillation.
0905 41 The following example reported in E. Amberger and H.
Boeters, "Preparation of Trisilylphosphine," Angew. Chem. Int.
Ed. 1, 52 (1962) illustrates the preparation of another preferred I formula II dopant, trisilylphosphine, (SiH 3 3
P:
Example 13 Trisilylphosphine is prepared in 55% yield by the reaction of monobromosilane with potassium dihydrophosphide (KPH 2 using a 1:1 molar ratio. The reaction mixture (solvent: dimethyl ether, frozen) is gradually warmed. The reaction begins at -120 0 C and is finished at -40 0 C. Ether, phosphine and unreacted silyl bromide can easily be separated from the trisilylphosphine by high-vacuum distillation.
The following example reported in the Handbook of Preparative Inorganic Chemistry, G. Braver, Ed., Academic Press, N.Y.
(1963) at pages 219-220, illustrates the preparation of a preferred formula III dopant of the present invention, boron trifluoride (BF 3 Example 14 A mixture of 80 g. of dried or, preferably, melted KBF 4 and 30 g. of B 2 0 3 is heated to about 600 0 C in an inclined iron tub (40 cm. long, 3 cm. diameter), which is sealed at one end. The other end of the iron tube is closed by a flange sealed with a copper gasket. An appr. 10-mm. diameter iron tube is welded into an opening in the flange and is connected to a drying tube filled .CARRErTT
JINNER
TnCCT. N.W.
o.c.ooo 42 aj-oaso
I
with glass wool, which acts as a dust filler. The drying tube is Sin turn joined to a quartz or glass trap cooled in liquid nitrogen. The apparatus ends in a drying tube filled with freshly dried KF. The yield is 17 g. of BF 3 This can be purified by 'repeated fractional distillation.
Another preferred formula III dopant difluoroborane (BHF 2 is prepared by the pyrolysis of diborane (B 2
H
6 at 100°C in the presence of boron trifluoride (BF 3 T. D. Coyle, J. J. Ritter and T. C. Farrar, Proc. Cher.. Soc. (1964) 25. Small amounts of difluoroborane can also be formed by subjecting a mixture of diborane and boron trifluoride to an electrical discharge. L.
S.
Lynds, J. Chem. Phys. 42 (1965) 1124.
0* The following example reported in A. B. Burg and.H. I.
:Schlesinger, "Hydrides of Boron," JACS 59, 780 (1937) illustrates the preparation of another preferred formula III dopant of the *present invention, borane carbonyl (BH 3
CO).
Example
I
70.7 cc. of B 2
H
6 and 670 cc of CO were condensed into a 615 cc bomb tube at -210 0 C. The bomb was sealed off, removed from 1 0 the lower temperature bath, and inverted just as the diborane melted, in order that the liquid running down might .evaporate and mix thoroughly with the carbon monoxide. Adequate mixing was made still more certain by'allowing the tube to remain for ten hours or longer at room temperature, before the reaction was .HEN4DERSON
CARRET
UNNER
TrqCrr*N.w. ~.D~c~ro.1 DJ-os.1 43 carried on by a twenty-minute heating in a steam-bath. After the heating, the bomb was cooled to -196 0 C, and the contents introduced into the vacuum apparatus by means of the vacuum tube opener. 77.8 cc of BH 3 CO and 24.9 cc of B 2
H
6 were then isolated.
The following examples, (Examples 16-17) reflect proposed processes for manufacturing n-layers of p-i-n type photovoltaic devices in accordance with the present invention using the !dopants of formula II.
I Example 16 (Proposed) 0 Sj A 500 A hydrogenated amorphous silicon alloy n-layer is de-
I
**0 posited in a D.C. glow discharge using a cathode current density O2f of 0.12 ma/cm 2 a substrate temperature of 240 0 C, a total gas *pressue of 0.5 torr and a flow rate of 12 SCCM of 4% (SiH 3 3 As in SiH 4 and 88 SCCM SiH 4 Example 17 (Proposed) A 500 A hydrogenated amorphous silicon alloy n-layer is deposited in a D.C. glow discharge using a cathode current density l of 0.09 ma/cm', a substrate temperature of 220 0 C, a total gas pressure of 0.5 torr and a flow rate of 12 SCCM of 2% (SiH 3 3 P in SiH 4 5 SCCM (SiH 3 4 Ge and 83 SCCM SiH 4 The following examples, (Examples 18-19) reflect proposed o processes for manufacturing p-layers of p-i-n type photovoltaic devices in accordance with the present invention using the dopants of formula I.1I.
'ICES
.ENDERUON
GARREn-
NER
O.C 000 -66so S44 Example 18 (Proposed) A 100 A hydrogenated amorphous silicon alloy p-layer is deposited using a cathode current density of 0.14 ma/cm 2 a- substrate temperature of 240°C, a total gas pressure of 0.5 torr and a deposition gas mixture of 10 SCCM (SiH 3 4 C, 12 SCCM of 1.5% BF3 in SiH 4 and 78 SCCM SiH 4 Example 19 (Proposed) S A 100 A hydrogenated amorphous silicon alloy p-layer is deposited using a cathode current density of 0.14 ma/cm 2 a sub- 0 istrate temperature of 240 0 C, a total gas pressure of 0.5 torr and a flow rate of 50 SCCM CH 4 10 SCCM of 3% BH 2 CO in SiH 4 and SCCM SiH 4 Example 20 (Proposed) 0 A 100 A hydrogenated amorphous silicon alloy p-layer is deposited using a cathode current density of 0.14 ma/cm 2 a substrate temperature of 240 0 C, a total gas pressure of 0.5 torr and a flow rate of 50 SCCM CH 4 12 SCCM of 1.5% BHF 2 in SiH4 and 38 SCCM SiH 4 Example 21 (Proposed) 0 (A proposed example for forming an n-layer for a p-i-n type ;*.**!photovoltaic device by mercury-sensitized photochemical deposition using monosilylgermane as a deposition feedstock material and trisilylphosphine as a dopant).
,cc
I
(LNDERIOH I CARfET I
INER
Ccl. H.W.
o c.rooo0
I
Provide a flow of 5 SCCM of monosilylgermane, 12 SCCM of 4% trisilylphosphine and 83 SCCM of silane. Dilute this gas mixture with hydrogen and pre-mix with mercury vapor in a conventional, thermally-controlled mercury vaporizer maintained at about 50 0
C.
Introduce the resulting gas mixture into a deposition chamber.
Maintain the pressure of the deposition chamber at about torr. Maintain the temperature of the substrates in the deposi- !tion chamber at 240"C. Use a conventional low-pressure mercury lamp to radiate intense 1849- and 2537 A resonance lines mW/cm 2 at 3-cm distance, with the intensity ratio of 1849-2537 A 0 being 1/6) of light through a transparent quartz window between *l -the lamp and the subtrate to excite the mercury atoms which sub- *00I sequently activates the monosilylgermane, trisilylphosphine and silane by dehydrogenation. Let the resulting deposition proceed 0 Suntil a 500 A layer of negatively-doped hydrogenated amorphous silicon alloy has been deposited.
It will be apparent to those skilled in the art that various modifications. and variations can be made in the present invention without departing from the scope or spirit of the invention.
SjThus, it is intended that the present invention cover the modifications and variations of this invention provided that they come within the scope of the appended claims or their equivalents.
riCLi
CARRETT
'NER
tCC..W.
C. 10000 46 .a O I This application is divided from standard patent application No. 68839/87 (accepted under No. 604,227), and the entire disclosure in the specification, claims and drawings of the said standard patent application No.
o8839/87 as originally lodged is hereby incorporated by reference into the present application.
S
S
44
S
**5
S
47
Claims (16)
1. A process for preparing a negatively-doped hydrogenated amorphous silicon alloy by deposition of a negatively-doped hydrogenated amorphous silicon alloy film onto a substrate in a deposition chamber comprising the step of introducing into the deposition chamber during deposition a deposition gas mixture which includes one or more dopants having the formula: .i 3 (SiX 3 )m L X3- m f wherein L is a Group 5A atom selected from thz g. of phosphorous, arsenic, antimony or bismuth, X i. i, 9e*O halogen or mixtures thereof, and m is an integei ,en 1 S* and 3, inclusive.
2. The process of claim 3 wherein L is phosphorous or arsenic and X is hydrogen, fluorine or mixtures thereof. 9 S 3. The process of claim 2 wherein L is phosphorous, 9 X is hydrogen and m is 3. 0
4. The process of claim 2 wherein L is arsenic, X is m hydrogen and m is 3. 48 The process of claim 1 wherein said deposition is by glow discharge.
6. The process of claim 1 wheren said deposition is by D.C. glow discharge.
7. The process of claim 1 wherein said dopant comprises less than 1% by volume of the deposition gas mixture. S
8. An improved semiconductor device comprising one or more negatively-doped hydrogenated amorphous silicon alloy regions made using one or more dopants having the formula: (SiX 3 )m L X3-m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures the? j and m is an integer between 1 and 3, inclusive.
9. The semiloniductor device of claim 8 wherein said semiconductor device is a photovoltaic device. 0 49 A method of manufacturing a semiconductor device comprising depositing on a substrate one or more negatively-doped hydrogenated amorphous silicon alloy regions using one or more dopants having the formula: (SiX3)m L X 3 -m wherein L is a Group 5A atom selected fioa the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
11. A semiconductor device comprising one or more hydrogenated amorphous silicon regions wherein at least one of said regions is negatively-doped hydrogenated amorphous silicon alloy made by deposition in a deposition chamber by introducing into the deposition chamber a deposition gas mixture which includes one or mcre dopants having the formula: S(SiX 3 )m L X3-m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
12. The semiconductor device of claim 11 wherein said semiconductor device is a photovoltaic device. 50
13. A process for preparing a semiconductor device comprising the step of depositing on a substrate one or more negatively-doped hydrogenated amorphous silicon alloy regions, at least one of said regions being a negatively-doped hydrogenated amorphous silicon alloy made by introducing into a deposition chamber during deposition a deposition gas mixture which includes one or more dopants having the formula: (Si 3 )m L X3-m Swherein L is a Group 5A atom selected from the group of Boee B phosphorous, arsenic, antimony or bismuth, X is hydrogen, oBe halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive.
14. A photovoltaic device comprising a front contact, a back contact, and one or more hydrogenated amorphous silicon regions between said front and back contacts **P 6 wherein at least one of the iegions is a negatively-doped hydrogenated amorphous silicon alloy made by deposition in a deposition chamber by introducing into the deposition chamber a deposition gas mixture which includes one or more o dopants having the formula: (SiX 3 )m L X3-m wherein L is a Group 5A atom selected fiom the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, 51 halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive. A process for preparing a photovoltaic device comprising depositing one or more hydrogenated amorphous silicon alloy regions between a front and back -ontact wherein at least one or the regions is a negatively-doped hydrogenated amorphous silicon alloy made by deposition in a deposition chamber by introducing into the deposition S chamber a deposition gas mixture which includes one or more dopants having the formula: S(SiX 3 )m X3-m wherein L is a Group 5A atom selected from the group of phosphorous, arsenic, antimony or bismuth, X is hydrogen, halogen or mixtures thereof, and m is an integer between 1 and 3, inclusive. I 16. A process for preparing a negatively-doped hydrogenated amorphous silicon alloy, substantially as hereinbefore described, and with reference to the examples 5 given and the accompanying drawings. a
17. An improved semiconductor device comprising one or more negatively-doped hydrogenated amorphous silicon alloy regions, substantially as hereinbefore described and 52 with reference to the examples gi-Ten and the accompanying drawings.
18. A method of manufa'turing a semiconductor device substantially as hereinbefore described and with reference to the examples given and the accompanying drawings.
19. A semiconductor device comprising one or more hydrogenated amorphous silicon regions, substantially as hereinbefore described and with reference to the examples given and the accompanying drawings. ,B e. 20. A process for preparing a semiconductor device, 1 substantially as hereinbefore described and with reference to the examples given and the accompanying drawings.
21. A photovoltaic device comprising a front contact, a back contact, and one or more hydrogenated amorphous S silicon regions between said front and back contacts, substantially as hereinbefore described and with reference to the examples given and the accompanying drawings.
22. A process for preparing a photovoltaic device comprising depositing one or more hydrogenated amorphous silicon alloy regions between a front and back contact, 53 substantially as hereinbef ore described and with reference to the examples given and the accompanying drawings. Dated this 30th day of November, 1990. SOLAREX CORPORATION By Its Patent Attorneys GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia *so 9. Doies 54
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83007386A | 1986-02-18 | 1986-02-18 | |
| US830073 | 1986-02-18 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU68839/87A Division AU604227B2 (en) | 1986-02-18 | 1987-02-16 | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6767190A AU6767190A (en) | 1991-03-14 |
| AU637852B2 true AU637852B2 (en) | 1993-06-10 |
Family
ID=25256250
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU68839/87A Ceased AU604227B2 (en) | 1986-02-18 | 1987-02-16 | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
| AU63080/90A Ceased AU640408B2 (en) | 1986-02-18 | 1990-09-24 | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
| AU67671/90A Ceased AU637852B2 (en) | 1986-02-18 | 1990-11-30 | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU68839/87A Ceased AU604227B2 (en) | 1986-02-18 | 1987-02-16 | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
| AU63080/90A Ceased AU640408B2 (en) | 1986-02-18 | 1990-09-24 | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0233613B1 (en) |
| JP (1) | JPH06103667B2 (en) |
| KR (1) | KR910001876B1 (en) |
| CN (1) | CN1024929C (en) |
| AT (1) | ATE120884T1 (en) |
| AU (3) | AU604227B2 (en) |
| CA (1) | CA1332343C (en) |
| DE (1) | DE3751209T2 (en) |
| EG (1) | EG18056A (en) |
| ES (1) | ES2074041T3 (en) |
| IE (1) | IE870367L (en) |
| IN (1) | IN168381B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EG18056A (en) * | 1986-02-18 | 1991-11-30 | Solarex Corp | Dispositif feedstock materials useful in the fabrication of hydrogenated amorphous silicon alloys for photo-voltaic devices and other semiconductor devices |
| EP0407088B1 (en) * | 1989-06-28 | 1998-05-06 | Mitsui Chemicals, Inc. | Method of forming an amorphous semiconductor film |
| DE3942058A1 (en) * | 1989-12-20 | 1991-06-27 | Phototronics Solartechnik Gmbh | New tetra:silyl methane and prepn. from aryl halo-silane - and carbon tetra:halide by redn. halogenation and hydrogenation, for amorphous silicon prodn. |
| DE3941997C1 (en) * | 1989-12-20 | 1991-01-24 | Phototronics Solartechnik Gmbh, 8011 Putzbrunn, De | Prepn. of di-, tri- or tetra-silyl-methane - by reacting aryl-halo-silane with di-, tri- or tetra -halo-methane in presence of reducing metal, and reacting prod. with hydrogen halide |
| EP1092755A4 (en) * | 1999-03-30 | 2004-12-22 | Jsr Corp | Coating composition |
| EP1421607A2 (en) | 2001-02-12 | 2004-05-26 | ASM America, Inc. | Improved process for deposition of semiconductor films |
| US7186630B2 (en) | 2002-08-14 | 2007-03-06 | Asm America, Inc. | Deposition of amorphous silicon-containing films |
| WO2006031240A1 (en) * | 2004-09-14 | 2006-03-23 | Arizona Board Of Regents | Hydride compounds with silicon and germanium core atoms and method of synthesizing same |
| US7312128B2 (en) * | 2004-12-01 | 2007-12-25 | Applied Materials, Inc. | Selective epitaxy process with alternating gas supply |
| WO2007062056A2 (en) * | 2005-11-23 | 2007-05-31 | The Arizona Board Of Regents, A Body Corporate Acting On Behalf Of Arizona State University | Silicon-germanium hydrides and methods for making and using same |
| EP1918966A1 (en) | 2006-11-02 | 2008-05-07 | Dow Corning Corporation | Method for forming a film with a graded bandgap by deposition of an amorphous material from a plasma |
| EP1919264A1 (en) | 2006-11-02 | 2008-05-07 | Dow Corning Corporation | Device for forming a film by deposition from a plasma |
| EP1918414A1 (en) | 2006-11-02 | 2008-05-07 | Dow Corning Corporation | Film deposition of amorphous films with a graded bandgap by electron cyclotron resonance |
| EP1923483A1 (en) | 2006-11-02 | 2008-05-21 | Dow Corning Corporation | Deposition of amorphous silicon films by electron cyclotron resonance |
| EP1918967B1 (en) | 2006-11-02 | 2013-12-25 | Dow Corning Corporation | Method of forming a film by deposition from a plasma |
| EP1918965A1 (en) | 2006-11-02 | 2008-05-07 | Dow Corning Corporation | Method and apparatus for forming a film by deposition from a plasma |
| DE102008016696A1 (en) | 2007-03-30 | 2008-12-11 | Rev Renewable Energy Ventures, Inc. | Plasma-assisted organofunctionalization of silicon tetrahalides or organohalosilanes |
| KR101501700B1 (en) * | 2007-04-02 | 2015-03-11 | 아리조나 보드 오브 리전트스, 아리조나주의 아리조나 주립대 대행법인 | Novel methods for making and using halosilylgermanes |
| NO342873B1 (en) | 2008-02-11 | 2018-08-20 | Inst Energiteknik | Semiconductor Component |
| CN103628044A (en) * | 2013-11-07 | 2014-03-12 | 中山市创科科研技术服务有限公司 | Device for preparing alpha-SiH film by photochemical vapor deposition |
| CN109686802A (en) * | 2018-11-09 | 2019-04-26 | 惠州凯珑光电有限公司 | A kind of packaging technology of electronic component and mould group |
| CN115117201B (en) * | 2022-06-24 | 2024-03-12 | 英利能源发展有限公司 | Silicon wafer phosphorus or boron doping method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344984A (en) * | 1980-06-24 | 1982-08-17 | Thomson-Csf | Process for producing a layer containing silicon |
| US4695331A (en) * | 1985-05-06 | 1987-09-22 | Chronar Corporation | Hetero-augmentation of semiconductor materials |
| AU6308090A (en) * | 1986-02-18 | 1990-12-13 | Solarex Corporation | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226897A (en) * | 1977-12-05 | 1980-10-07 | Plasma Physics Corporation | Method of forming semiconducting materials and barriers |
| JPS59182521A (en) * | 1983-04-01 | 1984-10-17 | Mitsui Toatsu Chem Inc | Formation of silicon hydrite thin film |
| JPS59200248A (en) * | 1983-04-28 | 1984-11-13 | Canon Inc | Production of image forming member |
| DE3429899A1 (en) * | 1983-08-16 | 1985-03-07 | Canon K.K., Tokio/Tokyo | METHOD FOR FORMING A DEPOSITION FILM |
| JPS60117712A (en) * | 1983-11-30 | 1985-06-25 | Toshiba Corp | Forming method of thin film |
| JPS60154521A (en) * | 1984-01-23 | 1985-08-14 | Semiconductor Energy Lab Co Ltd | Manufacture of silicon carbide film |
| JPH0669029B2 (en) * | 1984-07-25 | 1994-08-31 | 工業技術院長 | Method for forming p-type semiconductor thin film |
| GB2177119B (en) * | 1985-06-26 | 1989-04-26 | Plessey Co Plc | Organometallic chemical vapour deposition |
| IL79612A0 (en) * | 1985-08-09 | 1986-11-30 | American Cyanamid Co | Method and apparatus for the chemical vapor deposition of iii-v semiconductors utilizing organometallic and elemental pnictide sources |
| US4690830A (en) * | 1986-02-18 | 1987-09-01 | Solarex Corporation | Activation by dehydrogenation or dehalogenation of deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
-
1987
- 1987-02-10 EG EG77/87A patent/EG18056A/en active
- 1987-02-12 IE IE721419A patent/IE870367L/en unknown
- 1987-02-13 IN IN123/CAL/87A patent/IN168381B/en unknown
- 1987-02-13 ES ES87102090T patent/ES2074041T3/en not_active Expired - Lifetime
- 1987-02-13 EP EP87102090A patent/EP0233613B1/en not_active Expired - Lifetime
- 1987-02-13 DE DE3751209T patent/DE3751209T2/en not_active Expired - Fee Related
- 1987-02-13 AT AT87102090T patent/ATE120884T1/en active
- 1987-02-16 AU AU68839/87A patent/AU604227B2/en not_active Ceased
- 1987-02-16 CA CA000529799A patent/CA1332343C/en not_active Expired - Fee Related
- 1987-02-17 JP JP62034388A patent/JPH06103667B2/en not_active Expired - Lifetime
- 1987-02-18 CN CN87100729A patent/CN1024929C/en not_active Expired - Fee Related
- 1987-02-18 KR KR1019870001347A patent/KR910001876B1/en not_active IP Right Cessation
-
1990
- 1990-09-24 AU AU63080/90A patent/AU640408B2/en not_active Ceased
- 1990-11-30 AU AU67671/90A patent/AU637852B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344984A (en) * | 1980-06-24 | 1982-08-17 | Thomson-Csf | Process for producing a layer containing silicon |
| US4695331A (en) * | 1985-05-06 | 1987-09-22 | Chronar Corporation | Hetero-augmentation of semiconductor materials |
| AU6308090A (en) * | 1986-02-18 | 1990-12-13 | Solarex Corporation | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06103667B2 (en) | 1994-12-14 |
| CA1332343C (en) | 1994-10-11 |
| KR870008376A (en) | 1987-09-26 |
| IE870367L (en) | 1987-08-18 |
| DE3751209T2 (en) | 1995-08-10 |
| CN1024929C (en) | 1994-06-08 |
| IN168381B (en) | 1991-03-23 |
| ATE120884T1 (en) | 1995-04-15 |
| AU6883987A (en) | 1987-08-20 |
| ES2074041T3 (en) | 1995-09-01 |
| AU6767190A (en) | 1991-03-14 |
| AU604227B2 (en) | 1990-12-13 |
| CN87100729A (en) | 1987-11-25 |
| AU640408B2 (en) | 1993-08-26 |
| EP0233613B1 (en) | 1995-04-05 |
| AU6308090A (en) | 1990-12-13 |
| EG18056A (en) | 1991-11-30 |
| EP0233613A3 (en) | 1990-11-28 |
| EP0233613A2 (en) | 1987-08-26 |
| KR910001876B1 (en) | 1991-03-28 |
| JPS6351680A (en) | 1988-03-04 |
| DE3751209D1 (en) | 1995-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4910153A (en) | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices | |
| AU637852B2 (en) | Deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices | |
| US4690830A (en) | Activation by dehydrogenation or dehalogenation of deposition feedstock and dopant materials useful in the fabrication of hydrogenated amorphous silicon alloys for photovoltaic devices and other semiconductor devices | |
| US4598164A (en) | Solar cell made from amorphous superlattice material | |
| JP2539916B2 (en) | Photovoltaic element | |
| US4433202A (en) | Thin film solar cell | |
| IT8224631A1 (en) | A PIU PHOTOVOLTAIC DEVICE! SEMICONDUCTOR LAYERS AND PROCEDURE FOR ITS MANUFACTURING | |
| JPS58199710A (en) | P type amorphous oxygen and silicon alloy with improved wide band gap and application device | |
| JPH07123112B2 (en) | Method for depositing p-type amorphous semiconductor and method for manufacturing photoreceptor for electrophotography | |
| KR910002764B1 (en) | Amorphous semiconductor method and devices | |
| Gau et al. | Preparation of amorphous silicon films by chemical vapor deposition from higher silanes SinH2n+ 2 (n≳ 1) | |
| IE54573B1 (en) | Improved back reflector system and devices utilizing same | |
| US5151255A (en) | Method for forming window material for solar cells and method for producing amorphous silicon solar cell | |
| JP2692091B2 (en) | Silicon carbide semiconductor film and method for manufacturing the same | |
| US4777023A (en) | Preparation of silicon and germanium hydrides containing two different group 4A atoms | |
| Honma et al. | Optical and electronic properties of reactively sputtered amorphous GeN x: H | |
| JPH04192373A (en) | Photovoltaic element | |
| CA1213375A (en) | Semiconductor device having a body of amorphous silicon | |
| JP3487580B2 (en) | Deposited film forming method and deposited film forming apparatus | |
| JP2543498B2 (en) | Semiconductor thin film | |
| Fieselmann et al. | Preparation and Evaluation of p-Type Materials for a-Si Solar Cells Using DC Plasma Discharge Deposition of Trimethylboron (B (CH 3) 3) | |
| AU8339082A (en) | Amorphous semiconductor method and devices | |
| JPS63296381A (en) | Photoelectric conversion element | |
| JPH0563950B2 (en) | ||
| JPH0563951B2 (en) |